TW201418396A - Adhesive composition and film-shaped adhesive - Google Patents

Abstract

An adhesive composition including an epoxy resin and a polyamide resin is provided.

Description

Adhesive composition and film adhesive

This invention relates to an adhesive composition and a film adhesive.

Since the amide-based adhesive resin has heat resistance and adhesion to, for example, a temperature of 250 ° C, it can be used as an adhesive for a high-temperature process (see, for example, Patent Document 1).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2012/140740

In the case where the adhesive is to be used in the production step of an electronic material, it is preferable to provide an organic solvent which is not dissolved in a resist, a resist stripper, or the like used in the step. Performance, ie chemical resistance. However, the prior guanamine-based adhesive resin is dissolved in an organic solvent (for example, N-methylpyrrolidone, tetrahydrofuran, etc.) which is usually used in the above-mentioned use, and thus there is a limitation in use.

Accordingly, an object of the present invention is to provide an adhesive composition containing a polyamide resin excellent in chemical resistance and a film adhesive using the same.

The present invention provides an adhesive composition comprising an epoxy resin and a polyamide resin. Such an adhesive composition is excellent in heat resistance and chemical resistance. The adhesive composition of the present invention is particularly preferably used as an adhesive used in a temperature range of from 200 ° C to 270 ° C.

The polyamide resin preferably has a polyoxyalkanediyl group. The flexibility and adhesion of the adhesive composition are improved by the polyoxyalkylene group.

The polyamide resin preferably has a divalent aromatic ring group. The adhesion of the adhesive composition at a high temperature is further improved by the presence of a divalent aromatic ring group.

The polyamide resin preferably has a hydroxyl group. Thereby, the chemical resistance of the adhesive composition becomes better.

The polyamide resin may also have a 1,4-piperazinediyl group.

Further, the adhesive composition may be provided in the form of a film-like adhesive which is formed into a film.

According to the present invention, it is possible to provide an adhesive composition containing a polyamide resin excellent in chemical resistance and a film adhesive using the same.

The adhesive composition of the present embodiment contains a polyamide resin and an epoxy resin. Further, in the present invention, the term "adhesiveness" means that the storage elastic modulus (G') measured at 10 radians/second at a temperature of 20 ° C to 22 ° C is less than 3 × 10 ⁵ Pascal. (Dahlquist benchmark).

(polyamide resin)

The polyamide resin has a mercaptoamine group in the main chain, and the terminal of the main chain has an amine group, a carboxyl group, a carboxylic acid halide structure or a carboxylic anhydride structure. The end of the main chain may also be a group derived from a compound used in the modification described below. Further, examples of the carboxylic acid halide structure include a hydrazine halide group such as -COCl and -COBr, and a carboxylic acid anhydride structure means an acid anhydride group formed of a plurality of carboxyl groups.

The polyamide resin preferably has a structural unit represented by the following formula (1-1).

In the above formula (1-1), R ¹ and R ² represent a divalent organic group. R ^{1 is} preferably selected from the group consisting of a chain aliphatic compound, a cyclic aliphatic compound (including an alicyclic compound, a crosslinked cyclic compound, a spirocyclic hydrocarbon), a compound having a benzene ring (including naphthalene, anthracene, and fused tetraphenyl). a divalent organic group obtained by removing two hydrogen atoms from a compound in a group consisting of condensed polycyclic hydrocarbons such as hydrazine and hydrazine and benzene) and a heterocyclic compound.

R ^{2 is} preferably selected from the group consisting of a chain aliphatic compound, a cyclic aliphatic compound (including an alicyclic compound such as a compound having a methylene dicyclohexyl group, a crosslinked cyclic compound, a spirocyclic hydrocarbon), and a benzene ring. Compounds (including condensed polycyclic hydrocarbons such as naphthalene, anthracene, fused tetraphenyl, anthracene, fluorene, and benzene), heterocyclic compounds, polyalkylene oxides (including polyethylene oxide, polypropylene oxide), and polyorganoindenes a divalent organic group obtained by removing two hydrogen atoms from a compound or a halide thereof (fluoride or the like) of a group consisting of oxyalkylene (including polydimethyl siloxane or polymethylphenyl siloxane) . Further, the compound having a benzene ring as described above for the compound providing R ² contains 2,2-bis(4-phenoxyphenyl)propane and 2,2-bis(4-phenoxyphenyl). Bismuth, 2,2-bis(4-phenoxyphenyl)methane, 4,4'-bisphenoxybiphenyl, bis(4-phenoxyphenyl)ether, bis(4-phenoxybenzene) Ketone, 1,3-phenoxybenzene, 1,4-phenoxybenzene, 2,2'-dimethylbiphenyl, 5,5'-dimethyl-2,2'-sulfonyl -biphenyl, diphenyl ether, diphenyl hydrazine, benzophenone, diphenylmethane, and the like.

The polyamide resin preferably has a polyoxyalkylene group. When the polyamide resin contains a polyoxyalkylene group, the glass transition temperature of the adhesive composition is lowered, for example, it becomes easy to adhere at a low temperature such as room temperature, and the adhesiveness is excellent. The polyoxyalkylene group may be a group represented by the following formula (2). In the formula, n represents an integer of 2 or more, and R ⁶ represents an alkanediyl group. Here, the plurality of R ⁶ may be present in the same or different from each other.

In the above formula (2), R ⁶ may be linear or branched, preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 3 carbon atoms. Examples of R ⁶ include an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group. n is preferably 2 to 70, more preferably 6 to 33.

The polyoxyalkylene di-group is preferably composed of polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide-polypropylene oxide copolymer. Polyalkylene oxide-derived groups such as polyethylene glycol-polytetramethylene glycol copolymer, polypropylene glycol-polyether diol copolymer, polyethylene glycol-polypropylene glycol-polyether diol copolymer More preferably, it is a polyoxyethylene group or a polyoxypropylene-1,2-diyl group.

The method of introducing the polyoxyalkylene diamine into the polyamine resin is simply a use of a raw material having a polyoxyalkylene group in at least one raw material (polymerizable monomer).

The polyamine resin can be obtained, for example, by condensation polymerization of the monomer (A-1) represented by the following formula (A-1) and the monomer (B-1) represented by the following formula (B-1). . The carboxyl group of the monomer (A-1) can be converted into a fluorenyl chloride group to form a polydecylamine, which can also be produced by other methods. The monomer (A-1) and the monomer (B-1) may be used alone or in combination of two or more. Further, the definitions of R ¹ and R ² in the following formula (A-1) and formula (B-1) are preferably as described above.

HOOC-R ¹ -COOH (A-1)

H ₂ NR ² -NH ₂ (B-1)

Examples of the monomer (A-1) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, and 1,9-decane. Dicarboxylic acid, dodecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, etc. alkyl dicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, Aryl dicarboxylic acid such as 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4-methylhexahydrophthalic acid, 3-methyl six Hydrogen phthalic acid, 2-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 2-ethylhexahydrophthalic acid, methylnorbornane-2,3-di A dicarboxylic acid having a cyclohexane skeleton such as a carboxylic acid or methylnorbornane-3,4-dicarboxylic acid. In terms of improvement in heat resistance of the adhesive composition, an aryldicarboxylic acid is preferred.

The monomer (B-1) may, for example, be 2,2-bis[4-(4-aminophenoxy)phenyl]propane or bis[4-(3-aminophenoxy)phenyl]anthracene. Bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis[4-(4-amine Phenoxy)phenyl]methane, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4- (4-Aminophenoxy)phenyl]one, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2' - dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 5,5'-dimethyl-2,2 '-sulfonyl-biphenyl-4,4'-diamine, (4,4'-diamino)diphenyl ether, (4,4'-diamino)diphenylanthracene, (4,4 '-Diamino)benzophenone, (3,3'-diamino)benzophenone, (4,4'-diamino)diphenylmethane, (4,4'-diamino An aromatic diamine such as diphenyl ether, (3,3'-diamino)diphenyl ether or N,N'-bis(4-aminophenyl)piperazine, ethylidene diamine, and propyl group Diamines such as alkyl diamines, polyethylene oxide diamines, polyepoxys Polyalkylene oxide diamine such as propane diamine, (4,4'-diamino)dicyclohexylmethane, isophorone diamine, 1,4-diaminopropylpiperazine, [3,4-double Aliphatic diamines such as (1-aminoheptyl)-6-hexyl-5-(1-octenyl)]cyclohexene, dimethylaminomethylnordecene, polydimethyloxane diamine Isooxane diamine and the like.

The polyamine resin preferably has a polyoxyalkylene group, and more preferably a polyoxyalkylene group is present in the structure derived from the monomer (B-1) in the structural unit. That is, it is preferred that at least one of the monomer (A-1) and the monomer (B-1) has a polyoxyalkylene group, and more preferably at least one of the monomers (B-1) has a polyoxyalkylene group. base.

Therefore, the polyamide resin preferably has a structural unit obtained by condensation-polymerizing a polymerizable monomer containing a monomer having a polyoxyalkylene group and at least two amine groups (monomer (b-1)).

The content of the monomer (b-1) in the polymerizable monomer is preferably from 5 mol% to 20 mol%, more preferably from 7 mol% to 15 mol%, more preferably from 7 mol% to 15 mol%, based on the total amount of the monomers (B-1). 8 mol% to 10 mol%. The adhesive composition having a structural unit obtained by condensation polymerization of such a polymerizable monomer tends to be more excellent in adhesion to the adherend.

The monomer (b-1) is exemplified by a polyalkylene oxide polyamine. The polyalkylene oxide polyamine is preferably a polyalkylene oxide diamine or a polyalkylene oxide triamine, and such an amine can preferably be JEFFAMINE D-230 (HUNTSMAN, trade name), JEFFAMINE D- Polypropylene oxide diamine such as 400 (HUNTSMAN, trade name), JEFFAMINE D-2000 (HUNTSMAN, trade name), JEFFAMINE D-4000 (HUNTSMAN, trade name), JEFFAMINE ED-600 (HUNTSMAN, Copolymer diamine of polyethylene oxide and polyethylene oxide such as JEFFAMINE ED-900 (HUNTSMAN, trade name), JEFFAMINE EDR-148 (HUNTSMAN, trade name), JEFFAMINE EDR-176 (HUNTSMAN, commodity Polyamine (polyoxypropylene) such as polyethylene oxide diamine, JEFFAMINE T-403 (HUNTSMAN, trade name), JEFFAMINE T-3000 (HUNTSMAN, trade name), JEFFAMINE T-5000 (HUNTSMAN, trade name) Triglyceride triamine) and the like. These may be used alone or in combination of two or more.

Further, the polyamide resin preferably has an alicyclic structure. The adhesive composition having such a structure can suppress water absorption. The alicyclic structure may, for example, be a cyclohexyl group, a dicyclohexyl group, a methylene dicyclohexyl group, an isophorone group or a cyclohexyldimethyl group.

As the monomer having such an alicyclic structure, the monomer (A-1) can be exemplified by 1,4-dicarboxycyclohexane, and the monomer (BI) can be exemplified by bis(4-aminocyclohexyl)methane or the like. Carbaryl diamine and 1,3-bis(aminomethyl)cyclohexane. These may be used alone or in combination of two or more.

Further, the polyamide resin preferably has a methylene dicyclohexyl group in the structural unit, and more preferably a methylene dicyclohexyl group is present in the structure derived from the monomer (B-1) in the structural unit. That is, it is preferred that at least one of the monomer (A-1) and the monomer (B-1) has a methylene dicyclohexyl group, and more preferably at least one of the monomers (B-1) has a methylene group. Dicyclohexyl.

That is, the polyamide resin preferably has a structural unit obtained by condensation-polymerizing a polymerizable monomer containing a monomer having a methylene dicyclohexyl group and at least two amine groups (monomer (b-2)).

The content of the monomer (b-2) in the polymerizable monomer is preferably from 4 mol% to 28.5 mol%, more preferably from 8 mol% to 28.5 mol%, based on the total amount of the monomer (B-1). Preferably, it is 8 mol% to 20 mol%. The adhesive composition having a structural unit obtained by condensation-polymerizing such a polymerizable monomer can suppress water absorption and is more excellent in storage stability.

As the monomer (b-2), bis(4-aminocyclohexyl)methane can be preferably used.

As the polyamine resin, the structure derived from the monomer (B-1) in the structural unit preferably has a piperazine diyl group, more preferably a piperazine-N,N'-dipropyl group.

That is, the polyamine resin preferably has a condensation polymerization polymerization of a polymerizable monomer containing a monomer having a piperazine-N,N'-dipropyl group and at least two amine groups (monomer (b-3)). The structural unit obtained.

The content of the monomer (b-3) in the polymerizable monomer is not particularly limited, and the remaining amount after the application of the monomers (b-1) and (b-2) can be used in the maximum amount. According to the polyamine resin having a structural unit obtained by condensation polymerization of such a polymerizable monomer, an adhesive composition having excellent balance between heat resistance and adhesion can be obtained.

As the monomer (b-3), 1,4-bis(3-aminopropyl)piperazine can be preferably used.

The polyamide resin preferably has a hydroxyl group, more preferably a phenolic hydroxyl group. The chemical resistance is further improved by making the polyamide resin have a hydroxyl group. In the method of introducing a hydroxyl group into a polyamide resin, it is preferred to use a raw material having a hydroxyl group among at least one polymerizable monomer. Examples of the raw material having a hydroxyl group include hydroxyisophthalic acid.

Polyamine resin can be contained, for example, by including monomer (A-1) and monomer (B-1) Obtained by condensation polymerization of a polymerizable monomer. Further, an ester (A-1), a hydrazine halide or the like may be used instead of the monomer (A-1). The polymerizable monomer may also contain another monomer such as a diisocyanate (monomer (C-1)).

The method of the condensation polymerization is not particularly limited. For example, a method in which a polymerizable monomer is dissolved in a solvent and reacted at a reaction temperature of 0 ° C to 200 ° C and a reaction time of about 1 hour to 10 hours may be employed.

The solvent used in the condensation polymerization may, for example, be N-methylpyrrolidone, N-ethylpyrrolidone, N-methylbutylimine, dimethylfuran, toluene, N,N'-dimethyl Acetamide, hexamethylene phosphoniumamine, dimethyl alum, and the like. Among them, from the viewpoint of solubility of the resin, N-methylpyrrolidone is preferred.

Further, in the condensation polymerization, an accelerator such as a catalyst may be used for the purpose of promoting the condensation reaction. The amount of the accelerator added is preferably from 0.1 mol equivalent to 50 mol equivalent based on 10 mol equivalents of the polymerizable monomer. Examples of the accelerator include inorganic salts such as lithium chloride, calcium chloride, and calcium rhodanide; tertiary amines such as triethylamine and pyridine; tetramethylammonium chloride and tetraethylammonium bromide; A quaternary ammonium salt such as tetra-n-butylammonium bromide or the like.

The polyamine resin may be a polyamine resin (modified polyamine resin) which is modified by a polymer obtained by condensation polymerization, and the modified polyamine resin may be exemplified by an olefin-modified polyamine. The alkoxydecane modified polyamine, the decane modified polyimine, the epoxy modified polyamine, the polycarbonate modified polyamine, the isocyanate modified polyamine, and the like.

(epoxy resin)

From the viewpoint of efficiently crosslinking, the epoxy resin as the epoxy group-containing compound preferably has two or more epoxy groups. Specific examples can be exemplified by bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus containing epoxy resin, bisphenol S type epoxy resin, and alicyclic ring. Epoxy resin, aliphatic chain epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, diglycidyl ether of bisphenol, naphthalene A diglycidyl ether compound of a diol, a diglycidyl ether compound of a phenol, a diglycidyl ether compound of an alcohol, and an alkyl substituent, a halide, a hydride, or the like. These epoxy resins may be used alone or in combination of two or more.

The epoxy resin may also contain an epoxy hardener. Examples of the epoxy curing agent include a phenol type epoxy curing agent, a cresol type epoxy curing agent, and an ester type epoxy curing agent.

An imidazole may also be added to the hardening accelerator of the epoxy resin. Examples of the imidazoles include imidazole, 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-imidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazoline, naphthoimidazole, pyrazole, triazole, tetrazole, oxazole, pyridine, pyrazine, Pyridazine, pyrimidine, benzotriazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzene Pyrimidine hydrazine trimellitate and the like.

In the adhesive composition, relative to the solid content of the adhesive composition, The amount of the epoxy resin added to the polyamide resin is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 30% by mass, still more preferably 0.5% by mass to 20% by mass, and particularly preferably 1%. Mass%~15% by mass. If it is this range, sufficient chemical resistance can be maintained and the function as an adhesive improves.

The total content of the epoxy resin and the polyamide resin in the adhesive composition is preferably 40% by mass to 100% by mass, preferably 80% by mass to 100% by mass, based on the total amount of the adhesive composition. It is 100% by mass, that is, it is composed of an epoxy resin and a polyamide resin.

From the viewpoint of improving the adhesion, the adhesive composition may contain rosin resin, terpene resin, coumarone resin, phenol resin, styrene resin, aliphatic petroleum in the scope of the object of the invention. An adhesion-imparting agent such as a resin, an aromatic petroleum resin, or an aliphatic aromatic copolymer-based petroleum resin.

Further, the adhesive composition may contain an inorganic material such as alloy particles, glass particles or clay particles, or an organic material such as polymer particles. More specifically, examples of the alloy particles include a tin alloy, a lead alloy, an indium alloy, a zinc alloy, and a gold alloy. Examples of the glass include a lead system, a phosphate system, a boric acid system, a vanadate system, and a telluride. Fluoride-based glass, etc., examples of clay include: stevensite, montmorillonite, kaolinite, illite, smectite, chlorite, Vermiculite, etc., polymer particles include polyethylene terephthalate, polyacrylonitrile, fluororesin (polytetrafluoroethylene (PTFE)), epoxy resin, nylon, polyimine , polyamidoximine, polyethylene naphthalate, and the like.

The adhesive composition preferably contains no hardening catalyst such as an amine, a carboxylic acid, an acid anhydride or a peroxide, and the content of the hardening catalyst in the case of containing a hardening catalyst is preferably relative to the solid content of the adhesive composition. It is 1% by mass or less, more preferably 0.5% by mass or less.

The adhesive composition can also be provided in the form of a film. That is, a film-like adhesive containing the above-described adhesive composition is provided. The film-like adhesive may be a film-like adhesive comprising a layer of a single-layer or multi-layered adhesive composition, or a film-like adhesive layer having a single-layer or multi-layered adhesive composition formed on one or both sides of the support. Agent. An example of a method for producing a film adhesive is shown below.

For example, a film-like adhesive can be produced by applying an adhesive composition varnish containing an adhesive composition onto one side of a support and drying it.

Further, a film-like adhesive having a layer having an adhesive composition on both sides of the support can be produced by applying the adhesive composition varnish to both sides of the support and drying it.

Further, a layer of an adhesive composition formed by applying an adhesive composition varnish to a film such as a release film and drying it is transferred onto a support and transferred. Make a film adhesive.

Such a method of using a casting method is preferable in that it is easy to obtain a layer of a flat adhesive composition.

The thickness of the layer of the adhesive composition is preferably from 0.1 μm to 100 μm, more preferably from 1 μm to 50 μm. The thickness of the layer of the adhesive composition can be determined by the concentration of the adhesive composition in the adhesive composition varnish and the coating amount of the adhesive composition varnish. And adjust it appropriately.

The solvent used in the varnish of the adhesive composition is not particularly limited, and a diol solvent, a glycol ether solvent, a glycol ester solvent or the like is preferably used in terms of exhibiting good solubility of the adhesive composition.

Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, and triethylene glycol. Alcohol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene Alcohol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and the like. Further, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylbutylimine, N,N'-dimethylacetamide, dimethylformamide, etc. may also be used. . These solvents may be used alone or in combination of two or more.

The support is not particularly limited, and a material having heat resistance to a temperature of 200 ° C or higher is preferably used, and examples thereof include polyester, polyimine, polyamine, polyether oxime, polyphenylene sulfide, and polyether. A material of an organic material such as a ketone, a polyetheretherketone, a triacetonitrile cellulose, a polyether quinone, a polyethylene naphthalate, a polypropylene, an acrylic acid, a polystyrene, or a polycarbonate. Further, a support containing an inorganic material may be used, and a material containing an inorganic material such as aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, silicon wafer, or alloy may be used.

The adhesive composition of the present embodiment can be adhered at room temperature and has sufficient adhesion at 200 ° C to 270 ° C. The adhesive force of the adhesive composition of the present embodiment is preferably from 0.1 N/cm to 8.0 N/cm, more preferably from 0.3 N/cm to 5.0 N/cm, still more preferably from 0.5 N/cm to 2.0 N/cm. .

The preferred adherend for the adhesive composition is preferably a material having heat resistance to a temperature of 200 ° C or higher. The more specific adherend is not particularly limited as long as it can achieve the object of the invention, and examples thereof include polyamine resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate, and polynaphthalene. Polyester resin such as ethylene diformate, polytrimethylene terephthalate, poly(phthalic acid propylene dicarboxylate), polybutylene terephthalate or polybutylene naphthalate, polypropylene, polyethylene, etc. Polyolefin resin, acrylic resin, polyimide resin, polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, polyether ether ketone resin, triacetyl cellulose resin, polyether oxime resin, Polycarbonate resin, polyallylate resin or a mixed resin thereof, aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, ruthenium wafer and alloy. Among these materials, in terms of exhibiting high heat resistance, a polyester resin, a polyamide resin, a polyolefin resin, a polyimide resin, an acrylic resin, aluminum, magnesium, titanium, chromium, or the like is more preferable. Manganese, iron, nickel, zinc, tin, glass, copper and tantalum wafers.

[Examples]

(Synthesis Example 1)

In a separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 529.3 g of isophthaloyl dichloride and 75.7 g of terephthaloyl dichloride were used. , polypropylene glycol diamine (JEFFAMINE (registered trademark) D-2000, manufactured by HUNTSMAN) 447.2 g, 1,4-bis(3-aminopropyl)piperazine 462.8 g, and methylene cyclohexyldiamine (Wandamin HM) (registered trademark), manufactured by New Japan Physical and Chemical Corporation) 93.9 g was condensed and polymerized in 7609 g of N-methylpyrrolidone under ice-cooling for 1 hour, and condensed and polymerized at room temperature for 2 hours. After completion of the reaction, three times the amount of water was added to the reaction mixture, and the insoluble components were separated and dried, whereby a polyamide resin having a weight average molecular weight of 45,000 was obtained.

(Synthesis Example 2)

In a separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 55.7 g of isophthalic acid, 41.8 g of terephthalic acid, 15.3 g of 5-hydroxyisophthalic acid, and polypropylene glycol diamine ( JEFFAMINE (registered trademark) D-2000, manufactured by HUNTSMAN, the number of repeating units of polypropylene glycol: 33) 122.0 g, 1,4-bis(3-aminopropyl)piperazine 97.7 g, bis(4-amino ring) Hexyl)methane (Wandamin HM (registered trademark), manufactured by Nippon Chemical and Chemical Co., Ltd.) 12.8 g and iron powder 0.37 g in N-methylpyrrolidone 650 g, condensation polymerization was carried out for 10 hours while removing by-product water at 200 ° C . After completion of the reaction, the mixture was cooled, and 30.5 g of methylene diphenyl diisocyanate was added thereto, and the mixture was reacted at 160 ° C for 3 hours to obtain a NMP solution of a polyamine resin having a weight average molecular weight of 40,000.

(Example 1)

20 g of the polyamide resin of Synthesis Example 1 and 0.5 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) were dissolved in 32 g of dimethylacetamide to obtain a resin varnish.

Using the obtained resin varnish, the varnish was uniformly applied to a release PET (polyethylene terephthalate) film by a bar coater so that the thickness of the resin after drying became 20 μm. And dried at 160 ° C using a hot air dryer After 30 minutes, a film adhesive was formed.

(Example 2)

20 g of the polyamide resin of Synthesis Example 1 and 1.0 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) were dissolved in 32 g of dimethylacetamide to obtain a resin varnish.

Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.

(Example 3)

20 g of the polyamide resin of Synthesis Example 1 and 2.0 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) were dissolved in 32 g of dimethylacetamide to obtain a resin varnish.

Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.

(Example 4)

A resin varnish was obtained by dissolving 0.5 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) in an NMP solution containing 20 g of the polyamide resin of Synthesis Example 2.

Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.

(Example 5)

A resin varnish was obtained by dissolving 1.0 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) in an NMP solution containing 20 g of the polyamide resin of Synthesis Example 2.

Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.

(Example 6)

A resin varnish was obtained by dissolving 2.0 g of an epoxy resin (manufactured by Nippon Chemical Co., Ltd., trade name: NC-3000H) in an NMP solution containing 20 g of the polyamide resin of Synthesis Example 2.

Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.

(Example 7)

A resin varnish was obtained by dissolving 1.0 g of an epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., trade name: YDF-8170C) in an NMP solution containing 20 g of the polyamide resin of Synthesis Example 2.

Using the obtained resin varnish, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.

(Comparative Example 1)

20 g of the polyamide resin of Synthesis Example 1 was dissolved in 32 g of dimethylacetamide to obtain a resin varnish.

Using the obtained resin varnish, using a bar coater to dry the resin thickness The varnish was uniformly applied to the release PET film in such a manner that the degree was 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer to form a film-like adhesive.

(Comparative Example 2)

Using the resin varnish of Synthesis Example 2, the varnish was uniformly applied onto the release PET film by a bar coater so that the thickness of the resin after drying became 20 μm, and dried at 160 ° C for 30 minutes using a hot air dryer. A film adhesive is formed.

The film adhesives obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were evaluated as follows. The results are shown in Table 1.

[Chemical resistance evaluation]

Using the film-like adhesives produced in Examples 1 to 7 and Comparative Examples 1 and 2, a film (2 cm square) and a solvent (10 mL) shown in Table 1 were added to the glass vial. The mixture was stirred at 25 ° C for 8 hours using a mixing rotor. After the dissolution test, the film was taken out, and the chemical resistance was evaluated based on the residual film ratio of the mass basis after drying at 160 ° C for 30 minutes.

[Adhesion evaluation]

The film-like adhesives produced in Examples 1 to 7 and Comparative Examples 1 and 2 were respectively sandwiched between polyimine films (manufactured by TORAY-DUPONT, trade name: Kapton EN, thickness). 25 μm) and glass (manufactured by Nippon Electric Glass Co., Ltd., trade name: OA-10G) were pressure-bonded by a hand roller, and the adhesion after heating at 200 ° C for 30 minutes was measured. Specifically, one end of the film-like adhesive is peeled off from the glass plate and fixed to a tensile jig of a tensile tester. Press the glass plate against the stage, lift the film adhesive and bring it from the glass The plate was peeled off and subjected to a 90° peel test. The adhesion of the film adhesive was measured by this measurement.

[Heat resistance evaluation]

For the structure prepared in the adhesion evaluation, the following operations were repeated three times: heating from room temperature to 250 ° C, holding at this temperature for 30 minutes, and cooling at room temperature, observing the appearance at this time, and measuring the adhesion, The heat resistance was evaluated. As an evaluation item of heat resistance, the heat-resistant adhesive force is expressed as a percentage of a value obtained by dividing the adhesive force change rate by the adhesion force after the third operation by the adhesion force after the first operation.

NMP: N-methylpyrrolidone

THF: tetrahydrofuran

TMAH: 2.38% aqueous solution of tetramethylammonium hydroxide

In addition, the term "whitening" in the table means that the film is whitened by treatment with a solvent.

It is clear that the film-like adhesives of Examples 1 to 7 in which the polyamide resin and the epoxy resin are combined at a specific ratio can maintain heat resistance and improve chemical resistance. Further, it was confirmed that the chemical resistance of the film-like adhesives of Examples 4 to 7 using the polyamine resin having a hydroxyl group was further improved. Further, the film-like adhesives according to Examples 1 to 7 can be peeled off as determined by the measurement results of the adhesive force.

Claims (6)

An adhesive composition comprising an epoxy resin and a polyamide resin. The adhesive composition according to claim 1, wherein the polyamine resin has a polyoxyalkylene group. The adhesive composition according to claim 1 or 2, wherein the polyamine resin has a divalent aromatic ring group. The adhesive composition according to any one of claims 1 to 3, wherein the polyamine resin has a 1,4-piperazinediyl group. The adhesive composition according to any one of claims 1 to 4, wherein the polyamine resin has a hydroxyl group. A film-like adhesive which is obtained by forming an adhesive composition according to any one of the above-mentioned items of the first to fifth aspects of the invention.